1. Field of the Invention
The present invention relates to manufacturing of superconductor wire. More particularly, the invention relates to a method for manufacturing superconductor wire using a powder and rod process in conjunction with a multifilament niobium-tin design and a vanadium-gallium design that incorporates a plurality of niobium or niobium alloy or vanadium or vanadium filaments in a copper matrix.
2. Background
The conventional internal-tin process (IT) (see Eric Gregory, “Multifilamentary Superconducting Composites”, Concise Encyclopedia of Magnetic and Superconducting Materials, p. 332, 1992, Editor Jan Evetts, Pergamon Press, the contents of which are incorporated herein by reference in their entirety) and the conventional powder-in-tube process (PIT) (see C. A. M. van Beijen and J. D. Elen, IEEE Trans. Magn., MAG-15, 87, 1979, the contents of which are incorporated herein by reference in their entirety; and J. H. Lindenhovius, “SMI Activities and Plans on PIT Nb3Sn”, WAMS, Archamps, Mar. 23, 2004, the contents of which are incorporated herein by reference in their entirety) are the leading Nb3Sn conductor manufacturing approaches that have the potential to meet the High Energy Physics (HEP) goals of performance and cost for high field magnets such as the LHC luminosity upgrade. Along with the standard bronze process, schematics of both approaches are compared in FIG. 1. The main advantage of both the IT and PIT approaches is that they have more tin available (up to 20%) for Nb3Sn formation, where as the bronze approach is limited to 13% by weight. See A. Godeke, “Performance Boundaries in Nb3Sn Superconductors”, Ph.D. Thesis, 2005, University of Twente, Enshede, The Netherlands, the contents of which are incorporated herein by reference in their entirety.
Because of the higher availability of tin in both the IT and PIT approaches, significant progress has been achieved toward improving the non-Cu Jc (critical current density, Amps/mm2) performance. For example, the performance goal set by the conductor advisory group has been attained by the IT approach. See R. M. Scanlan and D. R. Dietderich, “Progress and Plans for the U.S. HEP Conductor Development Program”, IEEE Trans. On Appl. Super., Vol. 13, No. 12, p. 1536, June 2002, the contents of which are incorporated herein by reference in their entirety. The Jc (12 T, 4.2K) has been reported at or exceeding the 3,000 A/mm2. See J. A. Parrell et al., “High Field Nb3Sn Conductor Development at Oxford Superconducting Technology”, IEEE Trans. On Appl. Super., Vol. 13, No. 2, p. 3470, June 2003, the contents of which are incorporated herein by reference in their entirety. The non-Cu J achieved by the PIT approach is about 2,400 A/mm2 at 12 T. See Lindenhovius, supra. These high Jc performance characteristics are not possible with the bronze process due to lower tin availability.
Both the IT and PIT begin with a subelement. See Gregory, supra, and Godeke, supra. In the case of the IT, a Cu/Nb composite with solid niobium filaments imbedded in the copper matrix is hot extruded. After extrusion, the composite is gun drilled to form a hole at the center of the array of niobium filaments. A solid tin rod is then inserted into this composite and further processed to a size for restacking into a copper tube for design and fabrication of a multifilament conductor. The restacked billet is then cold drawn to final wire size.
In the case of the PIT approach, a copper-clad niobium tube is filled with an intermetallic NbSn2 powder compound, plus additional free tin and copper powder. The PIT subelement is then processed to a final restack size and, like the IT approach, is assembled into another copper tube to fabricate the final multifilament wire.
A weakness of both of the IT and PIT Nb3Sn processes is the fact that both approaches have to rely on a restack and cold drawing of the sub-elements due to the low melting temperature of tin. Such cold processing introduces complications and adds cost to the overall manufacture of advanced multifilament conductors. The complications inherent by cold restacking of sub-elements include lack of adequate bonding between sub-elements leading to piece length issues and higher cost of manufacture.
The cost to fabricate the IT Nb3Sn superconductors is on the order of $2 to $4 per meter. The cost associated with the PIT process is currently greater than $4 per meter. In contrast, the cost of state-of-the-art NbTi superconductors manufactured for the MRI industry is on the order of $0.50 to $1.00 per meter. See L. D. Cooley, A. K. Ghosh, and R. M. Scanlan, “Costs of high field superconducting magnet strands”, the contents of which are incorporated herein by reference in their entirety. If the cost of a Nb3Sn process could be reduced to the same level as the current state-of-the-art production levels of NbTi, then this higher performance conductor could become the conductor of choice for various commercial applications such as for example MR imaging and NMR spectroscopy. A low cost Nb3Sn conductor could allow magnet engineers new design opportunities toward reducing volume and weight of the overall magnet for a given applied magnetic field without sacrificing performance. Such a conductor would also have significant cost implications for large scale magnet projects such as upgrades for the Large Hadron Collider and the International Fusion machine. The fundamental issue is the nature of the low melting point of tin which inherently prevents the IT and the PIT multifilament processes to be hot extruded.
Earlier conductor developments have replaced the solid tin core of the sub-element in the IT process with salt cores. See W. Marancik, S. Hong, and R. Zhou, “Method for Producing Multifilamentary Niobium-Tin Superconductor”, U.S. Pat. No. 5,534,219, Jul. 9, 1996, the contents of which are incorporated herein by reference in their entirety. The sub-elements with the salt cores are then assembled into a multifilament array as schematically depicted in FIG. 1. This assembly is then hot extruded. The result is a fully bonded multifilament composite with removable inert salt cores. The inert salt cores are then dissolved with jets of water leaving behind longitudinally extended channels which are symmetrically distributed with reference to the transverse cross-section of the conductor. These channels are then filled with solid tin followed by further drawing the composite to a final wire size.
In practice, the size of the salt cores need to be relatively large after extrusion in order to dissolve the salts with jets of water. However, in modern high critical current IT conductors (for example RRP process, see Parrell, supra), it is desirable to increase the number of sub-elements such that the sub-element diameter is less than 100 microns at final wire diameter. This means the sub-elements with the salt cores would be too small for practical removal by water jet dissolution of the salts. Thus, the approach has been limited to a small number of sub-elements that may be designed into a multifilament billet.
Another recent IT development to reduce cost is the “Mono Element Internal Tin (MEIT) conductor. See B. A. Zeitlin, B. Gregory, J. Marte, M. Benz, T. Pyon, R. Scanlan, and D. Dietderich, “Results on Mono Element Internal Tin Nb3Sn Conductors (MEIT) with Nb7.5Ta and Nb(1Zr+0x) Filaments”, IEEE Trans. on Appl. Supercond., Vol. 15. No. 2, pp. 3393, June 2005, the contents of which are incorporated herein by reference in their entirety. The approach in this process reduces the steps by eliminating the final restack assembly of 19 or 37 IT subelements as depicted in the schematic of FIG. 1. In this approach, the sub-element is hot extruded and drawn into a multifilament wire. This approach takes advantage of the cost effective large scale assembly of the subelement in a similar manner to MRI production size NbTi billets. However, a weakness of this approach is the fact that after extrusion, the composite must be gun-drilled to form a hole for the insertion of solid tin. This operation is expensive since very few companies worldwide specialize in this operation for superconducting composites. Moreover, gun-drilling a long length rod could result in an off center hole and damage the inner filaments. Furthermore, MRI extruded production scale rods are about 3 to 4 inches in diameter, 30 feet long and not perfectly straight. Technology to drill a straight hole over such a length does not exist. An example of MEIT conductor design is shown in FIG. 2. The central region is filled with solid tin after the extrusion and is surrounded by an array of solid niobium filaments in a copper matrix.
In the PIT process, NbSn2 is the high tin source with about 72% tin by weight. While the melting point of NbSn2 is about 850° C. and may be considered for hot extrusion, it is an extremely hard compound and difficult to fracture, making this approach expensive to fabricate. Drawing this wire with PIT sub-elements containing the hard NbSn2 is difficult. The addition of ductile tin powder to micron size NbSn2 powder in early as well as more recent advanced designs of PIT wires enables processing long piece lengths of wire. See H. Krauth, A. Szulczyk, M. Thoener, and J. Lindenhovius, “Some Remarks on the Development of Commercial NbTi and Nb3Sn Superconductors”, in Progress on Nb-Based Superconductors, p. 91, Editors, K. Inoue, T. Takeuchi, and A. Kikuchi, Feb. 2-3, 2004, the contents of which are incorporated herein by reference in their entirety; C. V. Renaud, L. R. Motowidlo, and T. Wong, “Status of powder-in-tube Nb3Sn conductor development at Supercon”, IEEE Trans. Appl. Supercond., Vol. 13, No. 2, pp. 3490-3493, 2003, the contents of which are incorporated herein by reference in their entirety; and L. R. Motowidlo and G. M. Ozeryansky, “A Nb3Sn Conductor via Cu5Sn4 PIT Process for High Field Applications”, Adv. In Cryo. Eng., Vol. 54, p. 269, Jul. 16-20, 2007, the contents of which are incorporated herein by reference in their entirety. See also Matt Jewell et al., “Novel Approaches to Forming Nb3Sn”, 2005 Low Temperature Workshop, Napa, Calif., the contents of which are incorporated herein by reference in their entirety. Low temperature hydrostatic extrusion of PIT composite wires is presently being explored by groups in Europe to develop a large-scale process. However, reports so far indicate some difficulties with wire drawing. This may be due to the hard nature of NbSn2 and/or the lack of true bonding from low temperature hydrostatic extrusion. Moreover, it is still an expensive process due to the inherent high cost of the micron size Nb powder and the high cost of processing to form the intermetallic micron size NbSn2 powder. Furthermore, large scale hydrostatic presses are few worldwide with limited access for extrusion.
Referring to FIGS. 3a and 3b, in general, PIT Nb3Sn wire utilizing NbSn2 or Cu5Sn4 has shown a porous remnant of the core after final reaction and diffusion of the tin into the niobium tube. Another general feature of PIT Nb3Sn wires is large Al5 grains on the inner diameter of the reacted layer. Both features are undesirable. These general features have also been observed in recent PIT development work with FeSn2, Ni3Sn4, and YSn2 high-tin compounds. See L. R. Motowidlo, “An Extrudable Low-Cost Nb3Sn PIT Conductor for Applications for Applications to HEP Magnets”, Phase II SBIR ER84482, the contents of which are incorporated herein by reference in their entirety. FIGS. 3a and 3b illustrates a porosity and a large grain size of PIT Nb3Sn wire utilizing Cu5Sn4 cores.